Composition comprising pyrithione or a polyvalent metal salt of a pyrithione and furametpyr

ABSTRACT

The present invention relates to a composition comprising an effective amount of a pyrithione or a polyvalent metal salt of a pyrithione, an effective amount of furametpyr and an effective amount of a surfactant including a surfactant with an anionic functional group.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.60/875,230, filed Dec. 15, 2006.

FIELD

The present invention relates to a composition comprising an effectiveamount of a pyrithione or a polyvalent metal salt of pyrithione, aneffective amount of furametpyr, and an effective amount of a surfactantincluding a surfactant with an anionic functional group. Moreparticularly, the present invention relates to personal carecompositions and methods of treating microbial and fungal infections onthe skin or scalp. Even more particularly, the present invention relatesto methods for the treatment of dandruff and compositions, which provideimproved anti-dandruff activity.

BACKGROUND

Anti-dandruff shampoos typically incorporate an anti-dandruff active anddetergent surfactants. Among the type of anti-dandruff agents areparticulate, crystalline anti-dandruff agents, such as sulfur, seleniumsulfide and heavy metal salts of pyrithione. Soluble anti-dandruffagents, such as ketoconazole, are also commonly used.

Despite the options available, consumers still desire a shampoo thatprovides superior anti-dandruff efficacy versus currently marketedproducts; as such consumers have found that dandruff is still prevalent.Such a superior efficacy can be difficult to achieve.

Therefore, the use of other anti-fungal materials, such as furametpyr,in combination with pyrithione or a polyvalent metal salt of pyrithioneor in combination with other anti-microbial agents, is desirable toincrease the number of biological mechanisms simultaneously at work tocontrol the relevant fungal population.

SUMMARY

An embodiment of the present invention is directed to compositioncomprising an effective amount of a pyrithione or a polyvalent metalsalt of pyrithione, an effective amount of furametpyr, and an effectiveamount of a surfactant including a surfactant with an anionic functionalgroup.

These and other features, aspects, and advantages of the presentinvention will become evident to those skilled in the art from a readingof the present disclosure.

DETAILED DESCRIPTION

While the specification concludes with claims which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

It has now surprisingly been found, in accordance with the presentinvention, that anti-dandruff efficacy can be dramatically increased intopical compositions by the combination of an effective amount of apyrithione or a polyvalent metal salt of pyrithione and furametpyr.

An embodiment of the present invention provides topical skin and/or haircompositions which provide superior benefits from a pyrithione or apolyvalent metal salt of pyrithione in combination with furametpyr.Therefore an embodiment of the present invention provides topicalcompositions with improved benefits to the skin and scalp (e.g.,improved antidandruff efficacy). An embodiment of the present inventionalso provides a method for cleansing the hair and/or skin. These, andother benefits, will become readily apparent from the detaileddescription.

The present invention can comprise, consist of, or consist essentiallyof the essential elements and limitations of the invention describedherein, as well any of the additional or optional ingredients,components, or limitations described herein.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include carriers or by-products thatmay be included in commercially available materials.

The components and/or steps, including those, which may optionally beadded, of the various embodiments of the present invention, aredescribed in detail below.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

All ratios are weight ratios unless specifically stated otherwise.

All temperatures are in degrees Celsius, unless specifically statedotherwise.

Except as otherwise noted, all amounts including quantities,percentages, portions, and proportions, are understood to be modified bythe word “about”, and amounts are not intended to indicate significantdigits.

Except as otherwise noted, the articles “a”, “an”, and “the” mean “oneor more”

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. The compositionsand methods/processes of the present invention can comprise, consist of,and consist essentially of the essential elements and limitations of theinvention described herein, as well as any of the additional or optionalingredients, components, steps, or limitations described herein.

Herein, “effective” means an amount of a subject active high enough toprovide a significant positive modification of the condition to betreated. An effective amount of the subject active will vary with theparticular condition being treated, the severity of the condition, theduration of the treatment, the nature of concurrent treatment, and likefactors.

A. PYRITHIONE OR A POLYVALENT METAL SALT OF PYRITHIONE

In a preferred embodiment, the present may comprise pyrithione or apolyvalent metal salt of pyrithione. Any form of polyvalent metalpyrithione salts may be used, including platelet and needle structures.Preferred salts for use herein include those formed from the polyvalentmetals magnesium, barium, bismuth, strontium, copper, zinc, cadmium,zirconium and mixtures thereof, more preferably zinc. Even morepreferred for use herein is the zinc salt of 1-hydroxy-2-pyridinethione(known as “zinc pyrithione” or “ZPT”); more preferably ZPT in plateletparticle form, wherein the particles have an average size of up to about20 μm, preferably up to about 5 μm, more preferably up to about 2.5 μm.

Pyridinethione anti-microbial and anti-dandruff agents are described,for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No. 3,236,733; U.S.Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat. No. 4,345,080;U.S. Pat. No. 4,323,683; U.S. Pat. No. 4,379,753; and U.S. Pat. No.4,470,982.

It is further contemplated that when ZPT is used as the anti-microbialparticulate in the anti-microbial compositions herein, that anadditional benefit of hair growth or re-growth may be stimulated orregulated, or both, or that hair loss may be reduced or inhibited, orthat hair may appear thicker or fuller.

Zinc pyrithione may be made by reacting 1-hydroxy-2-pyridinethione(i.e., pyrithione acid) or a soluble salt thereof with a zinc salt (e.g.zinc sulfate) to form a zinc pyrithione precipitate, as illustrated inU.S. Pat. No. 2,809,971.

Preferred embodiments include from about 0.01% to about 5% of apyrithione or polyvalent metal salt of a pyrithione; more preferablyfrom about 0.1% to about 2%.

In embodiments having a particulate zinc material and a pyrithione orpolyvalent metal salt of pyrithione, the ratio of particulate zincmaterial to pyrithione or a polyvalent metal salt of pyrithione ispreferably from 5:100 to 10:1; more preferably from about 2:10 to 5:1;more preferably still from 1:2 to 3:1.

B. FURAMETPYR

In a preferred embodiment, the present invention may comprisefurametpyr. Furametpyr is a fungicide, and more specifically, furametpyris in the carboxamide class of anti-fungals. While not being bound bytheory, it is generally thought that the furametpyr mechanism is theinhibition of mitochondrial succinate oxidation.

Preferred embodiments of the present invention include from about 0.01%to about 3% of a furametpyr; more preferably from about 0.1% to about2%; more preferably still from about 0.2% to about 1.5%.

In the present invention, the combination of furametpyr with pyrithioneor the polyvalent metal salts of pyrithione may result in an increase inefficacy of a composition. In an embodiment of the present invention,such an increase may be an increase in efficacy for anti-dandruff.

In a further embodiment of the present invention, furametpyr may also beused in combination with other anti-microbial agents. Non-limitingexamples of other anti-microbial agents are ketoconazole, climbazole,octopirox, salicylic acid, coal tar, selenium sulfide and mixturesthereof. Such combinations of furametpyr with other anti-microbialagents, may result in an increase in efficacy of a composition, and evenmore particularly, may increase anti-dandruff efficacy.

Furametpyr generally comprises the following formula I:

Formula I

Formula: C₁₇H₂₀ClN₃O₂ CAS/Registry Number: 123572-88-3 CA Index Name:1H-Pyrazole-4-carboxamide, 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-(9CI) Trade Names: Limber ®

C. PARTICULATE ZINC MATERIAL

In a further embodiment of the present invention, the composition of thepresent invention may include an effective amount of a particulate zincmaterial. Preferred embodiments of the present invention include fromabout 0.001% to about 10% of a particulate zinc layered material; morepreferably from about 0.01% to about 7%; more preferably still fromabout 0.1% to about 5%.

Particulate zinc materials (PZM's) are zinc-containing materials whichremain mostly insoluble within formulated compositions. Many benefits ofPZM's require the zinc ion to be chemically available without beingsoluble, this is termed zinc lability. Physical properties of theparticulate material have the potential to impact lability. We havediscovered several factors which impact zinc lability and therefore haveled to development of more effective formulas based on PZM's.

Particle physical properties which have been found to be important tooptimize zinc lability of PZM's are morphology of the particle, surfacearea, crystallinity, bulk density, surface charge, refractive index, andpurity level and mixtures thereof. Control of these physical propertieshas been shown to increase product performance.

Examples of particulate zinc materials useful in certain embodiments ofthe present invention include the following:

Inorganic Materials: Zinc aluminate, Zinc carbonate, Zinc oxide andmaterials containing zinc oxide (i.e., calamine), Zinc phosphates (i.e.,orthophosphate and pyrophosphate), Zinc selenide, Zinc sulfide, Zincsilicates (i.e., ortho- and meta-zinc silicates), Zinc silicofluoride,Zinc Borate, Zinc hydroxide and hydroxy sulfate, zinc-containing layeredmaterials and combinations thereof.

Further, layered structures are those with crystal growth primarilyoccurring in two dimensions. It is conventional to describe layerstructures as not only those in which all the atoms are incorporated inwell-defined layers, but also those in which there are ions or moleculesbetween the layers, called gallery ions (A. F. Wells “StructuralInorganic Chemistry” Clarendon Press, 1975). Zinc-containing layeredmaterials (ZLM's) may have zinc incorporated in the layers and/or asmore labile components of the gallery ions.

Many ZLM's occur naturally as minerals. Common examples includehydrozincite (zinc carbonate hydroxide), basic zinc carbonate,aurichalcite (zinc copper carbonate hydroxide), rosasite (copper zinccarbonate hydroxide) and many related minerals that are zinc-containing.Natural ZLM's can also occur wherein anionic layer species such asclay-type minerals (e.g., phyllosilicates) contain ion-exchanged zincgallery ions. All of these natural materials can also be obtainedsynthetically or formed in situ in a composition or during a productionprocess.

Another common class of ZLM's, which are often, but not always,synthetic, is layered doubly hydroxides, which are generally representedby the formula [M²⁺ _(1−x)M⁺ _(x)(OH)₂]^(x+) A^(m−) _(x/m).nH₂O and someor all of the divalent ions (M²⁺) would be represented as zinc ions(Crepaldi, E L, Pava, P C, Tronto, J, Valim, J B J. Colloid Interfac.Sci. 2002, 248, 429-42).

Yet another class of ZLM's can be prepared called hydroxy double salts(Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem.1999, 38, 4211-6). Hydroxy double salts can be represented by thegeneral formula [M²⁺ _(1−x)M²⁺ _(1+x)(OH)_(3(1−y))]⁺ A^(n−)_((1=3y)/n).nH₂O where the two metal ion may be different; if they arethe same and represented by zinc, the formula simplifies to[Zn_(1+x)(OH)₂]^(2x+)2xA⁻.nH₂O. This latter formula represents (wherex=0.4) common materials such as zinc hydroxychloride and zinchydroxynitrate. These are related to hydrozincite as well wherein thedivalent anion is replaced by a monovalent anion. These materials canalso be formed in situ in a composition or in or during a productionprocess.

These classes of ZLM's represent relatively common examples of thegeneral category and are not intended to be limiting as to the broaderscope of materials which fit this definition.

Natural Zinc containing materials/Ores and Minerals. Sphalerite (zincblende), Wurtzite, Smithsonite, Franklinite, Zincite, Willemite,Troostite, Hemimorphite and combinations thereof.

Organic Salts. Zinc fatty acid salts (i.e., caproate, laurate, oleate,stearate, etc.), Zinc salts of alkyl sulfonic acids, Zinc naphthenate,Zinc tartrate, Zinc tannate, Zinc phytate, Zinc monoglycerolate, Zincallantoinate, Zinc urate, Zinc amino acid salts (i.e., methionate,phenylalinate, tryptophanate, cysteinate, etc) and combinations thereof.

Polymeric Salts. Zinc polycarboxylates (i.e., polyacrylate), Zincpolysulfate and combinations thereof.

Physically Adsorbed Forms. Zinc-loaded ion exchange resins, Zincadsorbed on particle surfaces, Composite particles in which zinc saltsare incorporated, (i.e., as core/shell or aggregate morphologies) andcombinations thereof.

Zinc Salts: zinc oxalate, zinc tannate, zinc tartrate, zinc citrate,zinc oxide, zinc carbonate, zinc hydroxide, zinc oleate, zinc phosphate,zinc silicate, zinc stearate, zinc sulfide, zinc undecylate, and thelike, and mixtures thereof; preferably zinc oxide or zinc carbonatebasic.

Commercially available sources of zinc oxide include Z-Cote and Z-CoteHPI (BASF), and USP I and USP II (Zinc Corporation of America).

Commercially available sources of zinc carbonate include Zinc CarbonateBasic (Cater Chemicals: Bensenville, Ill., USA), Zinc Carbonate(Shepherd Chemicals: Norwood, Ohio, USA), Zinc Carbonate (CPS UnionCorp.: New York, N.Y., USA), Zinc Carbonate (Elementis Pigments: Durham,UK), and Zinc Carbonate AC (Bruggemann Chemical: Newtown Square, Pa.,USA).

Basic zinc carbonate, which also may be referred to commercially as“Zinc Carbonate” or “Zinc Carbonate Basic” or “Zinc Hydroxy Carbonate”,is a synthetic version consisting of materials similar to naturallyoccurring hydrozincite. The idealized stoichiometry is represented byZn₅(OH)₆(CO₃)₂ but the actual stoichiometric ratios can vary slightlyand other impurities may be incorporated in the crystal lattice.

Particle Size of PZM

In an embodiment of the present invention, it is has been found that asmaller particle size is inversely proportional to relative zinclability

D (90) is the particle size which corresponds to 90% of the amount ofparticles are below this size. In an embodiment of the presentinvention, the particulate zinc material may have a particle sizedistribution wherein 90% of the particles are less than about 50microns. In a further embodiment of the present invention, theparticulate zinc material may have a particle size distribution wherein90% of the particles are less than about 30 microns. In yet a furtherembodiment of the present invention, the particulate zinc material mayhave a particle size distribution wherein 90% of the particles are lessthan about 20 microns.

Surface Area of PZM

In an embodiment of the present invention, there may be a directrelationship between surface area and relative zinc lability.

Increased particle surface area generally increases zinc lability due tokinetic factors. Particulate surface area can be increased by decreasingparticle size and/or altering the particle morphology to result in aporous particle or one whose overall shape deviates geometrically fromsphericity.

In an embodiment of the present invention, the basic zinc carbonate mayhave a surface area of greater than about 10 m²/gm. In a furtherembodiment, the basic zinc carbonate may have a surface area of greaterthan about 20 m²/gm. In yet a further embodiment of the presentinvention, the basic zinc carbonate may have a surface area of greaterthan about 30 m²/gm.

In an embodiment of the present invention, it has further surprisinglybeen found, that anti-dandruff efficacy can further be increased intopical compositions by the combination of an effective amount of apyrithione or a polyvalent metal salt of pyrithione and furametpyr, aneffective amount of a particulate zinc material with a surfactant withan anionic functional group and wherein the particulate zinc materialhas a specified zinc lability within a surfactant system. Zinc labilityis a measure of the chemical availability of zinc ion. Soluble zincsalts that do not complex with other species in solution have a relativezinc lability, by definition, of 100%. The use of partially solubleforms of zinc salts and/or incorporation in a matrix with potentialcomplexants generally lowers the zinc lability substantially below thedefined 100% maximum.

Labile zinc is maintained by choice of an effective particulate zincmaterial or formation of an effective particulate zinc material in-situby known methods.

An embodiment of the present invention provides a stable composition forparticulate zinc material dispersion where the zinc source resides in aparticulate form. It has been shown to be challenging to formulateaqueous systems containing a particulate zinc material, due to theparticulate zinc material's unique physical and chemical properties.Particulate zinc material may have a high density (approximately 3g/cm³), and needs to be evenly dispersed throughout the product and soit will not aggregate or settle. Particulate zinc material also has avery-reactive surface chemistry as well as the propensity to dissolve insystems with pH values below 6.5. Further, it has been surprisinglyfound in order for the particulate zinc material will remain as labile,in the presence of a surfactant with an anionic functional group.

A particulate zinc material with a solubility of less than 25% will havea measurable % soluble zinc value below a threshold value determined bythe weight percent and molecular weight of the zinc compound. Thetheoretical threshold value can be calculated by the following equation:

$\frac{\begin{matrix}{0.25*{{wt}.\mspace{11mu}\%}\mspace{11mu}\text{Zn}\mspace{14mu}{Compound}\mspace{14mu}{in}\mspace{14mu}{Composition}*} \\{{moles}\mspace{14mu}{of}\mspace{14mu}{Zinc}\mspace{14mu}{in}\mspace{14mu}{Compound}*65.39\mspace{11mu}\left( {{MW}\mspace{14mu}{of}\mspace{14mu}\text{Zn}} \right)}\end{matrix}}{{MW}\mspace{14mu}{of}\mspace{14mu}\text{Zn}\mspace{14mu}{Compound}}$

An embodiment of the present invention is directed to a compositioncomprising an effective amount of a pyrithione or a polyvalent metalsalt of pyrithione in combination with furametpyr; an effective amountof a particulate zinc material having a aqueous solubility of less thanabout 25% by weight at 25° C.; an effective amount of a surfactant withan anionic functional group; and water; wherein the pH of thecomposition is greater than about 6.5.

Zinc Binding Materials

Materials which have a high affinity for zinc and have the tendency toresult in the formation of insoluble complexes of zinc can foul thesurface of particulate zinc materials (PZM's). By “fouling” it is meantthe formation of an insoluble surface layer of the zinc binding material(ZBM) zinc salt which interferes with the kinetic lability of zinc fromthe base PZM material. The magnitude of negative effect of ZBM's is theproduct of the strength of association to zinc and the relative amountof the ZBM (relative to the PZM surface area). The PZM's can tolerate aportion of surface coverage without substantial inhibition of kineticlability.

Those materials with high potential to bind to the PZM surface are ZBM'sthat form only sparingly soluble salts with zinc in water. “Sparinglysoluble” refers to zinc salts with 1 gram (g)/100 g water solubility orless. These are the materials that form precipitated surface species onthe PZM that interfere with zinc lability. A summary of the solubilitiesof common zinc salts and further disclosure of zinc binding material isfound in U.S. application Ser. No. 11/216,520, filed Aug. 31, 2005 onpages 9-12 and incorporated by reference herein.

Many common raw materials may be sources for inadvertent ZBM's. In thecase of fatty acids, for example, any material which originates fromtriglycerides or fatty acids will likely contain some level of fattyacid ZBM in the raw material as used. Surfactants derived directly fromtriglycerides or those derived from fatty alcohols which are themselvesderived from triglycerides will contain varying levels of fatty acids.Other raw materials may contain relatively low levels of ZBM's that areadded for a secondary benefit. For example, citric acid is commonly usedfor pH control during raw material manufacture. It is not always obviousto the end user of a raw material if such ZBM's are present; thisinformation can be obtained from the manufacturer or analyzed directly.

Maximization of zinc lability from PZM's requires either completeavoidance of the presence of ZBM's or limiting the amount of thematerial to avoid complete coverage of the surface area of the PZM(i.e., saturation). An approximation of the amount of ZBM required tocompletely cover a PZM can be calculated based on effective surface areaof the PZM and a knowledge of how tightly the ZBM can pack on thesurface. The following example is illustrative of the process ofapproximating how much ZBM is certain to saturate and foul the entirePZM surface. It will be calculated for the general case in which a ZBMpacks on the surface in a manner analogous to a surfactant adsorbing atan oil-water interface. In this case, a common value for surface areaoccupied per molecule is 30 Å² (equivalent to 3×10⁻⁷μ²). It will becalculated per gram of a PZM with a measured surface area (SA, in m2/g):

${\frac{1\mspace{11mu} m^{2}Z\; B\; M}{g\mspace{11mu} P\; Z\;{M \cdot S}\; A\mspace{11mu} P\; Z\; M} \times \frac{Z\; B\; M\mspace{11mu}{molecule}}{3 \times 10^{- 7}µ^{2}\mspace{11mu} Z\; B\; M} \times \left( \frac{1 \times 10^{6}µ\; Z\; B\; M}{m\mspace{11mu} Z\; B\; M} \right)^{2} \times \frac{{mol}\mspace{11mu} Z\; B\; M}{6.02 \times 10^{23}\mspace{11mu}{molecules}\mspace{11mu} Z\; B\; M} \times \frac{1 \times 10^{6}\mspace{11mu}{µmol}\mspace{11mu} Z\; B\; M}{{mol}\mspace{11mu} Z\; B\; M}} = {5.5\mspace{11mu}{µmol}\mspace{11mu} Z\; B\; M\text{/}g\mspace{11mu} P\; Z\; M\text{-}S\; A\mspace{11mu} P\; Z\; M}$Thus, 5.5 micromoles of ZBM will saturate 1 g of a PZM with a surfacearea of 1 m²/g. Therefore, for the present invention, it is desirablethat the composition comprises less than 5.5 micromoles of a zincbinding material (ZBM) per gram (g) of a particulate zinc material(PZM)/per m²/g surface area of a particulate zinc material (PZM).For an example of zinc carbonate (a PZM) with a surface area of 30 m²/gand laurate as the ZBM, the calculation then becomes:

${\frac{30\mspace{11mu} m^{2}Z\; C}{g\mspace{11mu} Z\; C} \times \left( \frac{1 \times 10^{6}\mspace{11mu} µ\; Z\; C}{m\mspace{11mu} Z\; C} \right)^{2} \times \frac{L\; A\mspace{11mu}{molecule}}{3 \times 10^{- 7}\mspace{11mu} µ^{2}} \times \frac{{mole}\; L\; A}{6.02 \times 10^{23}\mspace{11mu}{molecules}\mspace{11mu} L\; A} \times \frac{200\mspace{11mu} g\mspace{11mu} L\; A}{{mole}\mspace{11mu} L\; A}} = {0.03\mspace{11mu} g\mspace{11mu} L\; A\text{/}g\mspace{11mu} Z\; C}$

Thus, approximately 0.03 g of laurate would saturate and foul thesurface of one gram of a zinc carbonate PZM with the specified surfacearea. Based on this type of analysis, other “fouling levels” can beestablished for the specific ZBM-PZM combination. However, this exampleprovides an approximation of the range of levels that need to becontrolled to assure zinc lability of the PZM.

More specifically, then, a formulation containing 1.6% of the zinccarbonate specified above would require a laurate level below 0.048%(480 ppm) to remain effective. This would represent the total lauratepresent, whether added directly or inadvertently entering a formula viaother raw material additions. This level also assumes there are no otherZBM's present; if there are, each needs to be considered separatelywhile maintaining a combined amount below surface saturation level.

D. TOPICAL CARRIER

In a preferred embodiment, the composition of the present invention isin the form of a topical composition, which includes a topical carrier.Preferably, the topical carrier is selected from a broad range oftraditional personal care carriers depending on the type of compositionto be formed. By suitable selections of compatible carriers, it iscontemplated that such a composition is prepared in the form of dailyskin or hair products including conditioning treatments, cleansingproducts, such as hair and/or scalp shampoos, body washes, handcleansers, water-less hand sanitizer/cleansers, facial cleansers and thelike.

In a preferred embodiment, the carrier is water. Preferably thecompositions of the present invention comprise from 40% to 95% water byweight of the composition; preferably from 50% to 85%, more preferablystill from 60% to 80%.

E. DETERSIVE SURFACTANT

The composition of the present invention includes a detersivesurfactant. The detersive surfactant component is included to providecleaning performance to the composition. The detersive surfactantcomponent in turn comprises anionic detersive surfactant, zwitterionicor amphoteric detersive surfactant, or a combination thereof. Suchsurfactants should be physically and chemically compatible with theessential components described herein, or should not otherwise undulyimpair product stability, aesthetics or performance.

Suitable anionic detersive surfactant components for use in thecomposition herein include those which are known for use in hair care orother personal care cleansing compositions. The concentration of theanionic surfactant component in the composition should be sufficient toprovide the desired cleaning and lather performance, and generally rangefrom about 2% to about 50%, preferably from about 8% to about 30%, morepreferably from about 10% to about 25%, even more preferably from about12% to about 22%.

Preferred anionic surfactants suitable for use in the compositions arethe alkyl and alkyl ether sulfates. These materials have the respectiveformulae ROSO₃M and RO(C₂H₄O)_(x)SO₃M, wherein R is alkyl or alkenyl offrom about 8 to about 18 carbon atoms, x is an integer having a value offrom 1 to 10, and M is a cation such as ammonium, alkanolamines, such astriethanolamine, monovalent metals, such as sodium and potassium, andpolyvalent metal cations, such as magnesium, and calcium.

Preferably, R has from about 8 to about 18 carbon atoms, more preferablyfrom about 10 to about 16 carbon atoms, even more preferably from about12 to about 14 carbon atoms, in both the alkyl and alkyl ether sulfates.The alkyl ether sulfates are typically made as condensation products ofethylene oxide and monohydric alcohols having from about 8 to about 24carbon atoms. The alcohols can be synthetic or they can be derived fromfats, e.g., coconut oil, palm kernel oil, tallow. Lauryl alcohol andstraight chain alcohols derived from coconut oil or palm kernel oil arepreferred. Such alcohols are reacted with between about 0 and about 10,preferably from about 2 to about 5, more preferably about 3, molarproportions of ethylene oxide, and the resulting mixture of molecularspecies having, for example, an average of 3 moles of ethylene oxide permole of alcohol, is sulfated and neutralized.

Other suitable anionic detersive surfactants are the water-soluble saltsof organic, sulfuric acid reaction products conforming to the formula[R¹—SO₃-M] where R¹ is a straight or branched chain, saturated,aliphatic hydrocarbon radical having from about 8 to about 24,preferably about 10 to about 18, carbon atoms; and M is a cationdescribed hereinbefore.

Still other suitable anionic detersive surfactants are the reactionproducts of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil or palm kernel oil; sodium or potassium salts of fattyacid amides of methyl tauride in which the fatty acids, for example, arederived from coconut oil or palm kernel oil. Other similar anionicsurfactants are described in U.S. Pat. Nos. 2,486,921; 2,486,922; and2,396,278.

Other anionic detersive surfactants suitable for use in the compositionsare the succinates, examples of which include disodiumN-octadecylsulfosuccinate; disodium lauryl sulfosuccinate; diammoniumlauryl; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate;diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodiumsulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic detersive surfactants include olefin sulfonateshaving about 10 to about 24 carbon atoms. In addition to the true alkenesulfonates and a proportion of hydroxy-alkanesulfonates, the olefinsulfonates can contain minor amounts of other materials, such as alkenedisulfonates depending upon the reaction conditions, proportion ofreactants, the nature of the starting olefins and impurities in theolefin stock and side reactions during the sulfonation process. A nonlimiting example of such an alpha-olefin sulfonate mixture is describedin U.S. Pat. No. 3,332,880.

Another class of anionic detersive surfactants suitable for use in thecompositions are the beta-alkyloxy alkane sulfonates. These surfactantsconform to the formula

where R¹ is a straight chain alkyl group having from about 6 to about 20carbon atoms, R² is a lower alkyl group having from about 1 to about 3carbon atoms, preferably 1 carbon atom, and M is a water-soluble cationas described hereinbefore.

Preferred anionic detersive surfactants for use in the compositionsinclude ammonium lauryl sulfate, ammonium laureth sulfate, triethylaminelauryl sulfate, triethylamine laureth sulfate, triethanolamine laurylsulfate, triethanolamine laureth sulfate, monoethanolamine laurylsulfate, monoethanolamine laureth sulfate, diethanolamine laurylsulfate, diethanolamine laureth sulfate, lauric monoglyceride sodiumsulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laurylsulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodiumlauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate and combinations thereof. In a further embodiment ofthe present invention, the anionic surfactant is preferably sodiumlauryl sulfate or sodium laureth sulfate.

Suitable amphoteric or zwitterionic detersive surfactants for use in thecomposition herein include those which are known for use in hair care orother personal care cleansing. Concentration of such amphotericdetersive surfactants preferably ranges from about 0.5% to about 20%,preferably from about 1% to about 10%. Non limiting examples of suitablezwitterionic or amphoteric surfactants are described in U.S. Pat. Nos.5,104,646 (Bolich Jr. et al.), 5,106,609 (Bolich Jr. et al.).

Amphoteric detersive surfactants suitable for use in the composition arewell known in the art, and include those surfactants broadly describedas derivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight or branched chain and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic group such as carboxy, sulfonate,sulfate, phosphate, or phosphonate. Preferred amphoteric detersivesurfactants for use in the present invention include cocoamphoacetate,cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate, and mixturesthereof.

Zwitterionic detersive surfactants suitable for use in the compositionare well known in the art, and include those surfactants broadlydescribed as derivatives of aliphatic quaternaryammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic group such as carboxy, sulfonate, sulfate, phosphate orphosphonate. Zwitterionics such as betaines are preferred.

The compositions of the present invention may further compriseadditional surfactants for use in combination with the anionic detersivesurfactant component described hereinbefore. Suitable optionalsurfactants include nonionic and cationic surfactants. Any suchsurfactant known in the art for use in hair or personal care productsmay be used, provided that the optional additional surfactant is alsochemically and physically compatible with the essential components ofthe composition, or does not otherwise unduly impair productperformance, aesthetics or stability. The concentration of the optionaladditional surfactants in the composition may vary with the cleansing orlather performance desired, the optional surfactant selected, thedesired product concentration, the presence of other components in thecomposition, and other factors well known in the art.

Non limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the compositions aredescribed in McCutcheon's, Emulsifiers and Detergents, 1989 Annual,published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678,2,658,072; 2,438,091; 2,528,378.

F. DISPERSED PARTICLES

The composition of the present invention may include dispersedparticles. In the compositions of the present invention, it ispreferable to incorporate at least 0.025% by weight of the dispersedparticles, more preferably at least 0.05%, still more preferably atleast 0.1%, even more preferably at least 0.25%, and yet more preferablyat least 0.5% by weight of the dispersed particles. In the compositionsof the present invention, it is preferable to incorporate no more thanabout 20% by weight of the dispersed particles, more preferably no morethan about 10%, still more preferably no more than 5%, even morepreferably no more than 3%, and yet more preferably no more than 2% byweight of the dispersed particles.

G. DISPERSED GEL NETWORK PHASE

In an embodiment of the present invention, the shampoo compositions ofthe present invention may comprise a dispersed gel network phasecomprising a fatty amphiphile. The gel network phase may be included inshampoo compositions of the present invention to provide conditioningbenefits. As used herein, the term “gel network” refers to a lamellar orvesicular solid crystalline phase which comprises at least one fattyamphiphile as specified below, at least one secondary surfactant asspecified below, and water or other suitable solvents. The lamellar orvesicular phase comprises bi-layers made up of a first layer comprisingthe fatty amphiphile and the secondary surfactant and alternating with asecond layer comprising the water or other suitable solvent. The term“solid crystalline”, as used herein, refers to the structure of thelamellar or vesicular phase which forms at a temperature below the chainmelt temperature of the layer in the gel network comprising the one ormore fatty amphiphiles, the chain melt temperature being at least about27° C. The chain melt temperature may be measured by differentialscanning calorimetry, a method of which is described in the Examplesbelow.

Gel networks which comprise, for example, fatty alcohols have been usedfor years in cosmetic creams and hair conditioners. Such cosmetic creamsand hair conditioners, however, typically contain very low amounts, ifany, of detersive surfactant. Thus, such known products do not provide acombination of cleansing and conditioning to the hair or skin.

Gel networks, generally, are further described by G. M. Eccleston,“Functions of Mixed Emulsifiers and Emulsifying Waxes in DermatologicalLotions and Creams”, Colloids and Surfaces A: Physiochem. and Eng.Aspects 123-124 (1997) 169-182; and by G. M Eccleston, “TheMicrostructure of Semisolid Creams”, Pharmacy International, Vol. 7,63-70 (1986).

In a further embodiment of the present invention, the dispersed gelnetwork phase is pre-formed. The term “pre-formed”, as used herein,means that the mixture of the fatty amphiphile, secondary surfactant,and water or other suitable solvent is substantially a solid crystallinephase when added to the other components of the shampoo composition.

According to this embodiment of the present invention, the gel networkcomponent of the present invention is prepared as a separate pre-mix,which, after being cooled, is subsequently incorporated with thedetersive surfactant and the other components of the shampoocomposition. More specifically, the gel network component of the presentinvention may be prepared by heating the fatty amphiphile, the secondarysurfactant, and water to a level in the range of about 75° C. to about90° C. and mixing. This mixture is cooled to a level in the range ofabout 27° C. to about 35° C. by, for example, passing the mixturethrough a heat exchanger. As a result of this cooling step, the fattyamphiphile and the secondary surfactant crystallize to form a solidcrystalline gel network.

As used herein, “fatty amphiphile” refers to a compound having ahydrophobic tail group of R₁ as defined below and a hydrophilic headgroup which does not make the compound water soluble, wherein thecompound also has a net neutral charge at the pH of the shampoocomposition. The term “water soluble”, as used herein, means that thematerial is soluble in water in the present composition. As used herein,“secondary surfactant” refers to one or more surfactants which arecombined with the fatty amphiphile and water to form the gel network ofthe present invention as a pre-mix separate from the other components ofthe shampoo composition. The secondary surfactant is separate from andin addition to the detersive surfactant component of the shampoocomposition. However, the secondary surfactant may be the same ordifferent type of surfactant or surfactants as that or those selectedfor the detersive surfactant component described herein. As used herein,the term “suitable solvent” refers to any solvent which can be used inthe place of or in combination with water in the formation of the gelnetwork of the present invention.

In a further embodiment of the present invention, a composition maycomprise an effective amount of a pyrithione or a polyvalent metal saltof a pyrithione or other anti-microbial active; furametpyr, an effectiveamount of a surfactant including a detersive surfactant with an anionicfunctional group, and a dispersed gel network phase comprising: i) atleast about 0.05% of one or more fatty amphiphiles, by weight of saidshampoo composition; ii) at least about 0.01% of one or more secondarysurfactants, by weight of said shampoo composition; and iii) water; andat least about 20% of an aqueous carrier, by weight of said shampoocomposition. In yet a further embodiment, the composition above mayfurther comprise an effective amount of a particulate zinc material.

U.S. patent application Ser. No. 11/228,770, filed on Sep. 16, 2005comprises further details on Dispersed Gel Networks, fatty amphiphiles,secondary surfactant, and water or suitable solvent, as described hereinand is incorporated by reference herein.

H. AQUEOUS CARRIER

The compositions of the present invention are typically in the form ofpourable liquids (under ambient conditions). The compositions willtherefore typically comprise an aqueous carrier, which is present at alevel of from about 20% to about 95%, preferably from about 60% to about85%. The aqueous carrier may comprise water, or a miscible mixture ofwater and organic solvent, but preferably comprises water with minimalor no significant concentrations of organic solvent, except as otherwiseincidentally incorporated into the composition as minor ingredients ofother essential or optional components.

I. ADDITIONAL COMPONENTS

The compositions of the present invention may further comprise one ormore optional components known for use in hair care or personal careproducts, provided that the optional components are physically andchemically compatible with the essential components described herein, ordo not otherwise unduly impair product stability, aesthetics orperformance. Individual concentrations of such optional components mayrange from about 0.001% to about 10%.

Non-limiting examples of optional components for use in the compositioninclude cationic polymers, conditioning agents (hydrocarbon oils, fattyesters, silicones), anti dandruff agents, suspending agents, viscositymodifiers, dyes, nonvolatile solvents or diluents (water soluble andinsoluble), pearlescent aids, foam boosters, additional surfactants ornonionic cosurfactants, pediculocides, pH adjusting agents, perfumes,preservatives, chelants, proteins, skin active agents, sunscreens, UVabsorbers, and vitamins, minerals, herbal/fruit/food extracts,sphingolipids derivatives or synthetical derivative, and clay.

1. Cationic Polymers

The compositions of the present invention may contain a cationicpolymer. Concentrations of the cationic polymer in the compositiontypically range from about 0.05% to about 3%, preferably from about0.075% to about 2.0%, more preferably from about 0.1% to about 1.0%.Preferred cationic polymers will have cationic charge densities of atleast about 0.4 meq/gm, preferably at least about 1.2 meq/gm, morepreferably at least about 1.5 meq/gm, but also preferably less thanabout 7 meq/gm, more preferably less than about 5 meq/gm. Herein,“cationic charge density” of a polymer refers to the ratio of the numberof positive charges on the polymer to the molecular weight of thepolymer. The average molecular weight of such suitable cationic polymerswill generally be between about 10,000 and 10 million, preferablybetween about 50,000 and about 5 million, more preferably between about100,000 and about 3 million.

Suitable cationic polymers for use in the compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. The cationicprotonated amines can be primary, secondary, or tertiary amines(preferably secondary or tertiary), depending upon the particularspecies and the selected pH of the composition. Any anionic counterionscan be used in association with the cationic polymers so long as thepolymers remain soluble in water, in the composition, or in a coacervatephase of the composition, and so long as the counterions are physicallyand chemically compatible with the essential components of thecomposition or do not otherwise unduly impair product performance,stability or aesthetics. Non limiting examples of such counterionsinclude halides (e.g., chloride, fluoride, bromide, iodide), sulfate andmethylsulfate.

Non limiting examples of such polymers are described in the CTFACosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley,and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

Non limiting examples of suitable cationic polymers include copolymersof vinyl monomers having cationic protonated amine or quaternaryammonium functionalities with water soluble spacer monomers such asacrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl anddialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinylcaprolactone or vinyl pyrrolidone.

Suitable cationic protonated amino and quaternary ammonium monomers, forinclusion in the cationic polymers of the composition herein, includevinyl compounds substituted with dialkylaminoalkyl acrylate,dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammoniumsalt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammoniumsalts, and vinyl quaternary ammonium monomers having cyclic cationicnitrogen-containing rings such as pyridinium, imidazolium, andquaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinylpyridinium, alkyl vinyl pyrrolidone salts.

Other suitable cationic polymers for use in the compositions includecopolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt(e.g., chloride salt) (referred to in the industry by the Cosmetic,Toiletry, and Fragrance Association, “CTFA”, as Polyquaternium-16);copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate(referred to in the industry by CTFA as Polyquaternium-11); cationicdiallyl quaternary ammonium-containing polymers, including, for example,dimethyldiallylammonium chloride homopolymer, copolymers of acrylamideand dimethyldiallylammonium chloride (referred to in the industry byCTFA as Polyquaternium 6 and Polyquaternium 7, respectively); amphotericcopolymers of acrylic acid including copolymers of acrylic acid anddimethyldiallylammonium chloride (referred to in the industry by CTFA asPolyquaternium 22), terpolymers of acrylic acid withdimethyldiallylammonium chloride and acrylamide (referred to in theindustry by CTFA as Polyquaternium 39), and terpolymers of acrylic acidwith methacrylamidopropyl trimethylammonium chloride and methylacrylate(referred to in the industry by CTFA as Polyquaternium 47). Preferredcationic substituted monomers are the cationic substituteddialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, andcombinations thereof. These preferred monomers conform the to theformula

wherein R¹ is hydrogen, methyl or ethyl; each of R², R³ and R⁴ areindependently hydrogen or a short chain alkyl having from about 1 toabout 8 carbon atoms, preferably from about 1 to about 5 carbon atoms,more preferably from about 1 to about 2 carbon atoms; n is an integerhaving a value of from about 1 to about 8, preferably from about 1 toabout 4; and X is a counterion. The nitrogen attached to R², R³ and R⁴may be a protonated amine (primary, secondary or tertiary), but ispreferably a quaternary ammonium wherein each of R², R³ and R⁴ are alkylgroups a non limiting example of which is polymethyacrylamidopropyltrimonium chloride, available under the trade name Polycare 133, fromRhone-Poulenc, Cranberry, N.J., U.S.A.

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, such as cationic cellulose derivatives andcationic starch derivatives. Suitable cationic polysaccharide polymersinclude those which conform to the formula

wherein A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual; R is an alkylene oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1,R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms, and the total number of carbon atoms for each cationicmoiety (i.e., the sum of carbon atoms in R1, R2 and R3) preferably beingabout 20 or less; and X is an anionic counterion as described inhereinbefore.

Preferred cationic cellulose polymers are salts of hydroxyethylcellulose reacted with trimethyl ammonium substituted epoxide, referredto in the industry (CTFA) as Polyquaternium 10 and available fromAmerchol Corp. (Edison, N.J., USA) in their Polymer LR, JR, and KGseries of polymers. Other suitable types of cationic cellulose includesthe polymeric quaternary ammonium salts of hydroxyethyl cellulosereacted with lauryl dimethyl ammonium-substituted epoxide referred to inthe industry (CTFA) as Polyquaternium 24. These materials are availablefrom Amerchol Corp. under the tradename Polymer LM-200.

Other suitable cationic polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride, specific examples of whichinclude the Jaguar series commercially available from Rhone-PoulencIncorporated and the N-Hance series commercially available from AqualonDivision of Hercules, Inc. Other suitable cationic polymers includequaternary nitrogen-containing cellulose ethers, some examples of whichare described in U.S. Pat. No. 3,962,418. Other suitable cationicpolymers include copolymers of etherified cellulose, guar and starch,some examples of which are described in U.S. Pat. No. 3,958,581. Whenused, the cationic polymers herein are either soluble in the compositionor are soluble in a complex coacervate phase in the composition formedby the cationic polymer and the anionic, amphoteric and/or zwitterionicdetersive surfactant component described hereinbefore. Complexcoacervates of the cationic polymer can also be formed with othercharged materials in the composition.

Techniques for analysis of formation of complex coacervates are known inthe art. For example, microscopic analyses of the compositions, at anychosen stage of dilution, can be utilized to identify whether acoacervate phase has formed. Such coacervate phase will be identifiableas an additional emulsified phase in the composition. The use of dyescan aid in distinguishing the coacervate phase from other insolublephases dispersed in the composition.

A potential side reaction that may occur during the quaternizationreaction of a cationic polymer production process is the formation oftrimethylamine (TMA). While not intending to be limited by theory, thepresence of TMA as an impurity in a cationic polymer containingcomposition at a pH greater than 6.8 may be found to be the source of anamine off-odor or fishy off-odor. It has surprisingly been discoveredthat pH has a significant effect on the level of TMA evolved into theheadspace of the composition—in particular, the level of TMA in theheadspace increases as the pH increases. Headspace is commonly referredto as the volume above a liquid or solid in a closed container. In turn,the level of amine off-odor can be found to be proportional to the levelof TMA present in the headspace. Additionally, it has been discoveredthat it is possible to reverse the TMA evolution into the headspace bylowering the pH of the composition, as demonstrated and discussed inU.S. application Ser. No. 11/216,520, filed Aug. 31, 2005 on pages 22-26and incorporated by reference herein.

Therefore, in order to produce an acceptable composition having a pH ofgreater than 6.8, which comprises a cationic polymer, with low to noamine off-odor, it has been discovered that it may be necessary to use acationic polymer which contains from no detectable TMA to low levels ofTMA. Levels of TMA from a cationic polymer can be measured using themethod as demonstrated and discussed in U.S. application Ser. No.11/216,520, filed Aug. 31, 2005 on pages 22-26 and incorporated byreference herein.

It has been discovered that compositions comprising cationic polymerswhich have levels of TMA, as measured, for example, in the methoddescribed above, below 45 ppm, preferably below 25 ppm, more preferablybelow 17 ppm, have no amine off-odor to low amine off-odor which hasbeen found to be acceptable.

Odor Evaluations

Expert olfactory panelists may be used to judge odor on any convenientscale. For example, a scale of 0 (no detectable amine off-odor) to 10(high amine off-odor) can be established and used for grading purposes.The establishment of such tests is a matter of routine, and variousother protocols can be devised according to the desires of anindividual.

2. Nonionic Polymers

Polyalkylene glycols having a molecular weight of more than about 1000are useful herein. Useful are those having the following generalformula:

wherein R⁹⁵ is selected from the group consisting of H, methyl, andmixtures thereof. Polyethylene glycol polymers useful herein are PEG-2M(also known as Polyox WSR® N-10, which is available from Union Carbideand as PEG-2,000); PEG-5M (also known as Polyox WSR® N-35 and PolyoxWSR® N-80, available from Union Carbide and as PEG-5,000 andPolyethylene Glycol 300,000); PEG-7M (also known as Polyox WSR® N-750available from Union Carbide); PEG-9M (also known as Polyox WSR® N-3333available from Union Carbide); and PEG-14 M (also known as Polyox WSR®N-3000 available from Union Carbide).3. Conditioning Agents

Conditioning agents include any material which is used to give aparticular conditioning benefit to hair and/or skin. In hair treatmentcompositions, suitable conditioning agents are those which deliver oneor more benefits relating to shine, softness, combability, antistaticproperties, wet-handling, damage, manageability, body, and greasiness.The conditioning agents useful in the compositions of the presentinvention typically comprise a water insoluble, water dispersible,non-volatile, liquid that forms emulsified, liquid particles. Suitableconditioning agents for use in the composition are those conditioningagents characterized generally as silicones (e.g., silicone oils,cationic silicones, silicone gums, high refractive silicones, andsilicone resins), organic conditioning oils (e.g., hydrocarbon oils,polyolefins, and fatty esters) or combinations thereof, or thoseconditioning agents which otherwise form liquid, dispersed particles inthe aqueous surfactant matrix herein. Such conditioning agents should bephysically and chemically compatible with the essential components ofthe composition, and should not otherwise unduly impair productstability, aesthetics or performance.

The concentration of the conditioning agent in the composition should besufficient to provide the desired conditioning benefits, and as will beapparent to one of ordinary skill in the art. Such concentration canvary with the conditioning agent, the conditioning performance desired,the average size of the conditioning agent particles, the type andconcentration of other components, and other like factors.

1. Silicones

The conditioning agent of the compositions of the present invention ispreferably an insoluble silicone conditioning agent. The siliconeconditioning agent particles may comprise volatile silicone,non-volatile silicone, or combinations thereof. Preferred arenon-volatile silicone conditioning agents. If volatile silicones arepresent, it will typically be incidental to their use as a solvent orcarrier for commercially available forms of non-volatile siliconematerials ingredients, such as silicone gums and resins. The siliconeconditioning agent particles may comprise a silicone fluid conditioningagent and may also comprise other ingredients, such as a silicone resinto improve silicone fluid deposition efficiency or enhance glossiness ofthe hair.

The concentration of the silicone conditioning agent typically rangesfrom about 0.01% to about 10%, preferably from about 0.1% to about 8%,more preferably from about 0.1% to about 5%, more preferably from about0.2% to about 3%. Non-limiting examples of suitable siliconeconditioning agents, and optional suspending agents for the silicone,are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646,and U.S. Pat. No. 5,106,609. The silicone conditioning agents for use inthe compositions of the present invention preferably have a viscosity,as measured at 25° C., from about 20 to about 2,000,000 centistokes(“csk”), more preferably from about 1,000 to about 1,800,000 csk, evenmore preferably from about 50,000 to about 1,500,000 csk, morepreferably from about 100,000 to about 1,500,000 csk.

The dispersed silicone conditioning agent particles typically have avolume average particle diameter ranging from about 0.01 μm to about 50μm, as measured using the Horiba LA-910 Particle Size Analyzer. TheHoriba LA-910 instrument uses the principles of low-angle FraunhoferDiffraction and Light Scattering to measure the particle size anddistribution in a dilute solution of particles. For small particleapplication to hair, the volume average particle diameters typicallyrange from about 0.01 μm to about 4 μm, preferably from about 0.01 μm toabout 2 μm, more preferably from about 0.01 μm to about 0.5 μm. Forlarger particle application to hair, the volume average particlediameters typically range from about 4 μm to about 50 μm, preferablyfrom about 6 μm to about 40 μm, and more preferably from about 10 μm toabout 35 μm.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, are foundin Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989).

a. Silicone Oils

Silicone fluids include silicone oils, which are flowable siliconematerials having a viscosity, as measured at 25° C., less than 1,000,000csk, preferably from about 5 csk to about 1,000,000 csk, more preferablyfrom about 100 csk to about 600,000 csk. Suitable silicone oils for usein the compositions of the present invention include polyalkylsiloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyethersiloxane copolymers, and mixtures thereof. Other insoluble, non-volatilesilicone fluids having hair conditioning properties may also be used.

Silicone oils include polyalkyl or polyaryl siloxanes which conform tothe following Formula (III):

wherein R is aliphatic, preferably alkyl or alkenyl, or aryl, R can besubstituted or unsubstituted, and x is an integer from 1 to about 8,000.Suitable R groups for use in the compositions of the present inventioninclude, but are not limited to: alkoxy, aryloxy, alkaryl, arylalkyl,arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, andhalogen-substituted aliphatic and aryl groups. Suitable R groups alsoinclude cationic amines and quaternary ammonium groups.

Preferred alkyl and alkenyl substituents are C₁ to C₅ alkyls andalkenyls, more preferably from C₁ to C₄, more preferably from C₁ to C₂.The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containinggroups (such as alkoxy, alkaryl, and alkamino) can be straight orbranched chains, and are preferably from C₁ to C₅, more preferably fromC₁ to C₄, even more preferably from C₁ to C₃, more preferably from C₁ toC₂. As discussed above, the R substituents can also contain aminofunctionalities (e.g. alkamino groups), which can be primary, secondaryor tertiary amines or quaternary ammonium. These include mono-, di- andtri-alkylamino and alkoxyamino groups, wherein the aliphatic portionchain length is preferably as described herein.

b. Amino and Cationic Silicones

Cationic silicone fluids suitable for use in the compositions of thepresent invention include, but are not limited to, those which conformto the general formula (V):(R₁)_(a)G_(3−a)—Si—(—OSiG₂)_(n)—(—OSiG_(b)(R₁)_(2−b)m)—O—SiG_(3−a)(R₁)_(a)wherein G is hydrogen, phenyl, hydroxy, or C₁-C₈ alkyl, preferablymethyl; a is 0 or an integer having a value from 1 to 3, preferably 0; bis 0 or 1, preferably 1; n is a number from 0 to 1,999, preferably from49 to 499; m is an integer from 1 to 2,000, preferably from 1 to 10; thesum of n and m is a number from 1 to 2,000, preferably from 50 to 500;R₁ is a monovalent radical conforming to the general formula CqH_(2q)L,wherein q is an integer having a value from 2 to 8 and L is selectedfrom the following groups:—N(R₂)CH₂—CH₂—N(R₂)₂—N(R₂)₂—N(R₂)₃A⁻—N(R₂)CH₂—CH₂—NR₂H₂A⁻wherein R₂ is hydrogen, phenyl, benzyl, or a saturated hydrocarbonradical, preferably an alkyl radical from about C₁ to about C₂₀, and A⁻is a halide ion.

An especially preferred cationic silicone corresponding to formula (V)is the polymer known as “trimethylsilylamodimethicone”, which is shownbelow in formula (VI):

Other silicone cationic polymers which may be used in the compositionsof the present invention are represented by the general formula (VII):

wherein R³ is a monovalent hydrocarbon radical from C₁ to C₁₈,preferably an alkyl or alkenyl radical, such as methyl; R⁴ is ahydrocarbon radical, preferably a C₁ to C₁₈ alkylene radical or a C₁₀ toC₁₈ alkyleneoxy radical, more preferably a C₁ to C₈ alkyleneoxy radical;Q⁻ is a halide ion, preferably chloride; r is an average statisticalvalue from 2 to 20, preferably from 2 to 8; s is an average statisticalvalue from 20 to 200, preferably from 20 to 50. A preferred polymer ofthis class is known as UCARE SILICONE ALE 56™, available from UnionCarbide.

c. Silicone Gums

Other silicone fluids suitable for use in the compositions of thepresent invention are the insoluble silicone gums. These gums arepolyorganosiloxane materials having a viscosity, as measured at 25° C.,of greater than or equal to 1,000,000 csk. Silicone gums are describedin U.S. Pat. No. 4,152,416; Noll and Walter, Chemistry and Technology ofSilicones, New York: Academic Press (1968); and in General ElectricSilicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76.Specific non-limiting examples of silicone gums for use in thecompositions of the present invention include polydimethylsiloxane,(polydimethylsiloxane) (methlylvinylsiloxane) copolymer,poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane)copolymer and mixtures thereof.

d. High Refractive Index Silicones

Other non-volatile, insoluble silicone fluid conditioning agents thatare suitable for use in the compositions of the present invention arethose known as “high refractive index silicones,” having a refractiveindex of at least about 1.46, preferably at least about 1.48, morepreferably at least about 1.52, more preferably at least about 1.55. Therefractive index of the polysiloxane fluid will generally be less thanabout 1.70, typically less than about 1.60. In this context,polysiloxane “fluid” includes oils as well as gums.

The high refractive index polysiloxane fluid includes those representedby general Formula (III) above, as well as cyclic polysiloxanes such asthose represented by Formula (VIII) below:

wherein R is as defined above, and n is a number from about 3 to about7, preferably from about 3 to about 5.

The high refractive index polysiloxane fluids contain an amount ofaryl-containing R substituents sufficient to increase the refractiveindex to the desired level, which is described herein. Additionally, Rand n must be selected so that the material is non-volatile.

Aryl-containing substituents include those which contain alicyclic andheterocyclic five and six member aryl rings and those which containfused five or six member rings. The aryl rings themselves can besubstituted or unsubstituted.

Generally, the high refractive index polysiloxane fluids will have adegree of aryl-containing substituents of at least about 15%, preferablyat least about 20%, more preferably at least about 25%, even morepreferably at least about 35%, more preferably at least about 50%.Typically, the degree of aryl substitution will be less than about 90%,more generally less than about 85%, preferably from about 55% to about80%.

Preferred high refractive index polysiloxane fluids have a combinationof phenyl or phenyl derivative substituents (more preferably phenyl),with alkyl substituents, preferably C₁-C₄ alkyl (more preferablymethyl), hydroxy, or C₁-C₄ alkylamino (especially —R¹NHR²NH2 whereineach R¹ and R² independently is a C₁-C₃ alkyl, alkenyl, and/or alkoxy).

When high refractive index silicones are used in the compositions of thepresent invention, they are preferably used in solution with a spreadingagent, such as a silicone resin or a surfactant, to reduce the surfacetension by a sufficient amount to enhance spreading and thereby enhancethe glossiness (subsequent to drying) of hair treated with thecompositions.

Silicone fluids suitable for use in the compositions of the presentinvention are disclosed in U.S. Pat. No. 2,826,551, U.S. Pat. No.3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433, andSilicon Compounds, Petrarch Systems, Inc. (1984).

e. Silicone Resins

Silicone resins may be included in the silicone conditioning agent ofthe compositions of the present invention. These resins are highlycross-linked polymeric siloxane systems. The cross-linking is introducedthrough the incorporation of trifunctional and tetrafunctional silaneswith monofunctional or difunctional, or both, silanes during manufactureof the silicone resin.

Silicone materials and silicone resins in particular, can convenientlybe identified according to a shorthand nomenclature system known tothose of ordinary skill in the art as “MDTQ” nomenclature. Under thissystem, the silicone is described according to presence of varioussiloxane monomer units which make up the silicone. Briefly, the symbol Mdenotes the monofunctional unit (CH₃)₃SiO_(0.5); D denotes thedifunctional unit (CH₃)₂SiO; T denotes the trifunctional unit(CH₃)SiO_(1.5); and Q denotes the quadra- or tetra-functional unit SiO₂.Primes of the unit symbols (e.g. M′, D′, T′, and Q′) denote substituentsother than methyl, and must be specifically defined for each occurrence.

Preferred silicone resins for use in the compositions of the presentinvention include, but are not limited to MQ, MT, MTQ, MDT and MDTQresins. Methyl is a preferred silicone substituent. Especially preferredsilicone resins are MQ resins, wherein the M:Q ratio is from about0.5:1.0 to about 1.5:1.0 and the average molecular weight of thesilicone resin is from about 1000 to about 10,000.

The weight ratio of the non-volatile silicone fluid, having refractiveindex below 1.46, to the silicone resin component, when used, ispreferably from about 4:1 to about 400:1, more preferably from about 9:1to about 200:1, more preferably from about 19:1 to about 100:1,particularly when the silicone fluid component is a polydimethylsiloxanefluid or a mixture of polydimethylsiloxane fluid andpolydimethylsiloxane gum as described herein. Insofar as the siliconeresin forms a part of the same phase in the compositions hereof as thesilicone fluid, i.e. the conditioning active, the sum of the fluid andresin should be included in determining the level of siliconeconditioning agent in the composition.

2. Organic Conditioning Oils

The conditioning component of the compositions of the present inventionmay also comprise from about 0.05% to about 3%, preferably from about0.08% to about 1.5%, more preferably from about 0.1% to about 1%, of atleast one organic conditioning oil as the conditioning agent, eitheralone or in combination with other conditioning agents, such as thesilicones (described herein).

a. Hydrocarbon Oils

Suitable organic conditioning oils for use as conditioning agents in thecompositions of the present invention include, but are not limited to,hydrocarbon oils having at least about 10 carbon atoms, such as cyclichydrocarbons, straight chain aliphatic hydrocarbons (saturated orunsaturated), and branched chain aliphatic hydrocarbons (saturated orunsaturated), including polymers and mixtures thereof. Straight chainhydrocarbon oils preferably are from about C₁₂ to about C₁₉. Branchedchain hydrocarbon oils, including hydrocarbon polymers, typically willcontain more than 19 carbon atoms.

Specific non-limiting examples of these hydrocarbon oils includeparaffin oil, mineral oil, saturated and unsaturated dodecane, saturatedand unsaturated tridecane, saturated and unsaturated tetradecane,saturated and unsaturated pentadecane, saturated and unsaturatedhexadecane, polybutene, polydecene, and mixtures thereof. Branched-chainisomers of these compounds, as well as of higher chain lengthhydrocarbons, can also be used, examples of which include highlybranched, saturated or unsaturated, alkanes such as thepermethyl-substituted isomers, e.g., the permethyl-substituted isomersof hexadecane and eicosane, such as2,2,4,4,6,6,8,8-dimethyl-10-methylundecane and2,2,4,4,6,6-dimethyl-8-methylnonane, available from PermethylCorporation. Hydrocarbon polymers such as polybutene and polydecene. Apreferred hydrocarbon polymer is polybutene, such as the copolymer ofisobutylene and butene. A commercially available material of this typeis L-14 polybutene from Amoco Chemical Corporation. The concentration ofsuch hydrocarbon oils in the composition preferably range from about0.05% to about 20%, more preferably from about 0.08% to about 1.5%, andeven more preferably from about 0.1% to about 1%.

b. Polyolefins

Organic conditioning oils for use in the compositions of the presentinvention can also include liquid polyolefins, more preferably liquidpoly-α-olefins, more preferably hydrogenated liquid poly-α-olefins.Polyolefins for use herein are prepared by polymerization of C₄ to aboutC₁₄ olefenic monomers, preferably from about C₆ to about C₁₂.

Non-limiting examples of olefenic monomers for use in preparing thepolyolefin liquids herein include ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,branched chain isomers such as 4-methyl-1-pentene, and mixtures thereof.Also suitable for preparing the polyolefin liquids are olefin-containingrefinery feedstocks or effluents. Preferred hydrogenated α-olefinmonomers include, but are not limited to: 1-hexene to 1-hexadecenes,1-octene to 1-tetradecene, and mixtures thereof.

c. Fatty Esters

Other suitable organic conditioning oils for use as the conditioningagent in the compositions of the present invention include, but are notlimited to, fatty esters having at least 10 carbon atoms. These fattyesters include esters with hydrocarbyl chains derived from fatty acidsor alcohols (e.g. mono-esters, polyhydric alcohol esters, and di- andtri-carboxylic acid esters). The hydrocarbyl radicals of the fattyesters hereof may include or have covalently bonded thereto othercompatible functionalities, such as amides and alkoxy moieties (e.g.,ethoxy or ether linkages, etc.).

Specific examples of preferred fatty esters include, but are not limitedto: isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexylpalmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecylstearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate,lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyloleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyladipate.

Other fatty esters suitable for use in the compositions of the presentinvention are monocarboxylic acid esters of the general formula R′COOR,wherein R′ and R are alkyl or alkenyl radicals, and the sum of carbonatoms in R′ and R is at least 10, preferably at least 22.

Still other fatty esters suitable for use in the compositions of thepresent invention are di- and tri-alkyl and alkenyl esters of carboxylicacids, such as esters of C₄ to C₈ dicarboxylic acids (e.g. C₁ to C₂₂esters, preferably C₁ to C₆, of succinic acid, glutaric acid, and adipicacid). Specific non-limiting examples of di- and tri-alkyl and alkenylesters of carboxylic acids include isocetyl stearyol stearate,diisopropyl adipate, and tristearyl citrate.

Other fatty esters suitable for use in the compositions of the presentinvention are those known as polyhydric alcohol esters. Such polyhydricalcohol esters include alkylene glycol esters, such as ethylene glycolmono and di-fatty acid esters, diethylene glycol mono- and di-fatty acidesters, polyethylene glycol mono- and di-fatty acid esters, propyleneglycol mono- and di-fatty acid esters, polypropylene glycol monooleate,polypropylene glycol 2000 monostearate, ethoxylated propylene glycolmonostearate, glyceryl mono- and di-fatty acid esters, polyglycerolpoly-fatty acid esters, ethoxylated glyceryl monostearate, 1,3-butyleneglycol monostearate, 1,3-butylene glycol distearate, polyoxyethylenepolyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylenesorbitan fatty acid esters.

Still other fatty esters suitable for use in the compositions of thepresent invention are glycerides, including, but not limited to, mono-,di-, and tri-glycerides, preferably di- and tri-glycerides, morepreferably triglycerides. For use in the compositions described herein,the glycerides are preferably the mono-, di-, and tri-esters of glyceroland long chain carboxylic acids, such as C₁₀ to C₂₂ carboxylic acids. Avariety of these types of materials can be obtained from vegetable andanimal fats and oils, such as castor oil, safflower oil, cottonseed oil,corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil,sesame oil, lanolin and soybean oil. Synthetic oils include, but are notlimited to, triolein and tristearin glyceryl dilaurate.

Other fatty esters suitable for use in the compositions of the presentinvention are water insoluble synthetic fatty esters. Some preferredsynthetic esters conform to the general Formula (IX):

wherein R¹ is a C₇ to C₉ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenylgroup, preferably a saturated alkyl group, more preferably a saturated,linear, alkyl group; n is a positive integer having a value from 2 to 4,preferably 3; and Y is an alkyl, alkenyl, hydroxy or carboxy substitutedalkyl or alkenyl, having from about 2 to about 20 carbon atoms,preferably from about 3 to about 14 carbon atoms. Other preferredsynthetic esters conform to the general Formula (X):

wherein R² is a C₈ to C₁₀ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenylgroup; preferably a saturated alkyl group, more preferably a saturated,linear, alkyl group; n and Y are as defined above in Formula (X).

Specific non-limiting examples of suitable synthetic fatty esters foruse in the compositions of the present invention include: P-43 (C₈-C₁₀triester of trimethylolpropane), MCP-684 (tetraester of3,3-diethanol-1,5-pentadiol), MCP 121 (C₈-C₁₀ diester of adipic acid),all of which are available from Mobil Chemical Company.

3. Other Conditioning Agents

Also suitable for use in the compositions herein are the conditioningagents described by the Procter & Gamble Company in U.S. Pat. Nos.5,674,478, and 5,750,122. Also suitable for use herein are thoseconditioning agents described in U.S. Pat. Nos. 4,529,586 (Clairol),4,507,280 (Clairol), 4,663,158 (Clairol), 4,197,865 (L'Oreal), 4,217,914(L'Oreal), 4,381,919 (L'Oreal), and 4,422,853 (L'Oreal).

4. Additional Components

The compositions of the present invention may further include a varietyof additional useful components. Preferred additional components includethose discussed below:

1. Other Anti-Microbial Actives

The compositions of the present invention may further include one ormore anti-fungal or anti-microbial actives in addition to the metalpyrithione salt actives. Suitable anti-microbial actives include coaltar, sulfur, whitfield's ointment, castellani's paint, aluminumchloride, gentian violet, octopirox (piroctone olamine), ciclopiroxolamine, undecylenic acid and it's metal salts, potassium permanganate,selenium sulfide, sodium thiosulfate, propylene glycol, oil of bitterorange, urea preparations, griseofulvin, 8-Hydroxyquinoline clioquinol,thiabendazole, thiocarbamates, haloprogin, polyenes, hydroxypyridone,morpholine, benzylamine, allylamines (such as terbinafine), tea treeoil, clove leaf oil, coriander, palmarosa, berberine, thyme red,cinnamon oil, cinnamic aldehyde, citronellic acid, hinokitol, ichthyolpale, Sensiva SC-50, Elestab HP-100, azelaic acid, lyticase,iodopropynyl butylcarbamate (IPBC), isothiazalinones such as octylisothiazalinone and azoles, and combinations thereof. Preferredanti-microbials include itraconazole, ketoconazole, selenium sulphideand coal tar.

a. Azoles

Azole anti-microbials include imidazoles such as benzimidazole,benzothiazole, bifonazole, butaconazole nitrate, climbazole,clotrimazole, croconazole, eberconazole, econazole, elubiol,fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole,lanoconazole, metronidazole, miconazole, neticonazole, omoconazole,oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole,thiazole, and triazoles such as terconazole and itraconazole, andcombinations thereof. When present in the composition, the azoleanti-microbial active is included in an amount from about 0.01% to about5%, preferably from about 0.1% to about 3%, and more preferably fromabout 0.3% to about 2%, by weight of the composition. Especiallypreferred herein is ketoconazole.

b. Selenium Sulfide

Selenium sulfide is a particulate anti-dandruff agent suitable for usein the anti-microbial compositions of the present invention, effectiveconcentrations of which range from about 0.1% to about 4%, by weight ofthe composition, preferably from about 0.3% to about 2.5%, morepreferably from about 0.5% to about 1.5%. Selenium sulfide is generallyregarded as a compound having one mole of selenium and two moles ofsulfur, although it may also be a cyclic structure that conforms to thegeneral formula Se_(x)S_(y), wherein x+y=8. Average particle diametersfor the selenium sulfide are typically less than 15 μm, as measured byforward laser light scattering device (e.g. Malvern 3600 instrument),preferably less than 10 μm. Selenium sulfide compounds are described,for example, in U.S. Pat. No. 2,694,668; U.S. Pat. No. 3,152,046; U.S.Pat. No. 4,089,945; and U.S. Pat. No. 4,885,107.

c. Sulfur

Sulfur may also be used as a particulate anti-microbial/anti-dandruffagent in the anti-microbial compositions of the present invention.Effective concentrations of the particulate sulfur are typically fromabout 1% to about 4%, by weight of the composition, preferably fromabout 2% to about 4%.

d. Keratolytic Agents

The present invention may further comprise one or more keratolyticagents such as Salicylic Acid.

Additional anti-microbial actives of the present invention may includeextracts of melaleuca (tea tree) and charcoal. The present invention mayalso comprise combinations of anti-microbial actives. Such combinationsmay include octopirox and zinc pyrithione combinations, pine tar andsulfur combinations, salicylic acid and zinc pyrithione combinations,octopirox and climbasole combinations, and salicylic acid and octopiroxcombinations, and mixtures thereof.

2. Hair Loss Prevention and Hair Growth Agent

The present invention may further comprise materials useful for hairloss prevention and hair growth stimulants or agents. Examples of suchagents are Anti-Androgens such as Propecia, Dutasteride, RU5884;Anti-Inflammatories such as Glucocortisoids, Macrolides, Macrolides;Anti-Microbials such as Zinc pyrithione, Ketoconazole, Acne Treatments;Immunosuppressives such as FK-506, Cyclosporin; Vasodilators such asminoxidil, Aminexil® and combinations thereof.

3. Sensates

The present invention may further comprise topical sensate materialssuch as terpenes, vanilloids, alkyl amides, natural extracts andcombinations thereof as demonstrated and disclosed in U.S. applicationSer. No. 11/216,520, filed Aug. 31, 2005 on page 39 and incorporated byreference herein.

4. Humectant

The compositions of the present invention may contain a humectant. Thehumectants herein are selected from the group consisting of polyhydricalcohols, water soluble alkoxylated nonionic polymers, and mixturesthereof, as demonstrated and disclosed in U.S. application Ser. No.11/216,520, filed Aug. 31, 2005 on pages 39-40 and incorporated byreference herein. Humectants, when used herein, are preferably used atlevels of from about 0.1% to about 20%, more preferably from about 0.5%to about 5%.

5. Suspending Agent

The compositions of the present invention may further comprise asuspending agent at concentrations effective for suspendingwater-insoluble material in dispersed form in the compositions or formodifying the viscosity of the composition. Such concentrations rangefrom about 0.1% to about 10%, preferably from about 0.3% to about 5.0%.Suspending agents useful herein include anionic polymers and nonionicpolymers. Suspending agents useful herein are further demonstrated anddisclosed in U.S. application Ser. No. 11/216,520, filed Aug. 31, 2005on pages 40-42 and incorporated by reference herein.

6. Other Optional Components

The compositions of the present invention may contain also vitamins andamino acids such as: water soluble vitamins such as vitamin B1, B2, B6,B12, C, pantothenic acid, pantothenyl ethyl ether, panthenol, biotin,and their derivatives, water soluble amino acids such as asparagine,alanin, indole, glutamic acid and their salts, water insoluble vitaminssuch as vitamin A, D, E, and their derivatives, water insoluble aminoacids such as tyrosine, tryptamine, and their salts.

The compositions of the present invention may also contain pigmentmaterials such as inorganic, nitroso, monoazo, disazo, carotenoid,triphenyl methane, triaryl methane, xanthene, quinioline, oxazine,azine, anthraquinone, indigoid, thionindigoid, quinacridone,phthalocianine, botanical, natural colors, including: water solublecomponents such as those having C. I. Names.

The compositions of the present invention may also contain antimicrobialagents which are useful as cosmetic biocides and antidandruff agentsincluding: water soluble components such as piroctone olamine, waterinsoluble components such as 3,4,4′-trichlorocarbanilide (triclocarban),triclosan and zinc pyrithione.

The compositions of the present invention may also contain chelatingagents.

J. COORDINATING COMPOUND HAVING A LOG ZN BINDING CONSTANT

In an embodiment of the present invention, the composition furthercomprises a coordinating compound with a Log Zn binding constant in arange sufficient to maintain zinc bioavailability, as demonstrated anddisclosed in U.S. application Ser. No. 11/216,520, filed Aug. 31, 2005on pages 42-43 and incorporated by reference herein.

K. PH

Preferably, the pH of the present invention may be greater than about6.8. Further, the pH of the present invention may be in a range fromabout 6.8 to about 12, preferably from about 6.8 to about 10, morepreferably from about 6.8 to about 9, and even more preferably fromabout 6.8 to about 8.5.

L. METHOD FOR ASSESSMENT OF ZINC LABILITY IN ZINC-CONTAINING PRODUCTS

Zinc lability is a measure of the chemical availability of zinc ion.Soluble zinc salts that do not complex with other species in solutionhave a relative zinc lability, by definition, of 100%. The use ofpartially soluble forms of zinc salts and/or incorporation in a matrixwith potential complexants generally lowers the zinc labilitysubstantially below the defined 100% maximum.

Zinc lability is assessed by combining a diluted zinc-containingsolution or dispersion with the metallochromic dye xylenol orange (XO)and measurement of the degree of color change under specifiedconditions. The magnitude of color formation is proportional to thelevel of labile zinc. The procedure developed has been optimized foraqueous surfactant formulations but may be adapted to other physicalproduct forms as well.

A spectrophotometer is used to quantify the color change at 572 nm, thewavelength of optimum color change for XO. The spectrophotometer is setto zero absorbance at 572 nm utilizing a product control as close incomposition to the test product except excluding the potentially labileform of zinc. The control and test products are then treated identicallyas follows. A 50 μl product sample is dispensed into ajar and 95 ml ofdeaerated, distilled water are added and stirred. 5 mL of a 23 mg/mLxylenol orange stock solution at pH 5.0 is pipetted into the sample jar;this is considered time 0. The pH is then adjusted to 5.50±0.01 usingdilute HCl or NaOH. After 10.0 minutes, a portion of the sample isfiltered (0.45μ) and the absorbance measured at 572 nm. The measuredabsorbance is then compared to a separately measured control todetermine the relative zinc lability (zero TO 100%). The 100% labilitycontrol is prepared in a matrix similar to the test products bututilizing a soluble zinc material (such as zinc sulfate) incorporated atan equivalent level on a zinc basis. The absorbance of the 100% labilitycontrol is measured as above for the test materials. The relative zinclability is preferably greater than about 15%, more preferably greaterthan about 20%, and even more preferably greater than about 25%.

Using this methodology, the below examples demonstrate a material (basiczinc carbonate) that has intrinsically high lability in an anionicsurfactant system compared to one (ZnO) with low intrinsic lability.

Relative Zinc Relative Zinc Lability (%) Lability (%) In SimpleSurfactant In Water System¹ Lability Benefit Zinc Oxide 86.3 1.5 NOBasic zinc 100 37 YES carbonate ¹Simple surfactant system: 6% sodiumlauryl sulfate

M. PARTICLE SIZE DETERMINATION METHOD

Particle size analyses on zinc oxide and hydrozincite raw materials, asdemonstrated and disclosed in U.S. application Ser. No. 11/216,520,filed Aug. 31, 2005 on pages 44-45 are incorporated by reference herein.

N. SURFACE AREA METHODOLOGY

Surface area analysis as demonstrated and disclosed in U.S. applicationSer. No. 11/216,520, filed Aug. 31, 2005 on pages 45 are incorporated byreference herein.

O. METHODS OF USE

The compositions of the present invention may be used in directapplication to the skin or in a conventional manner for cleansing skinand hair and controlling microbial infection (including fungal, viral,or bacterial infections) on the skin or scalp. The compositions hereinare useful for cleansing the hair and scalp, and other areas of the bodysuch as underarm, feet, and groin areas and for any other area of skinin need of treatment. The present invention may be used for treating orcleansing of the skin or hair of animals as well. An effective amount ofthe composition, typically from about 1 g to about 50 g, preferably fromabout 1 g to about 20 g of the composition, for cleansing hair, skin orother area of the body, is topically applied to the hair, skin or otherarea that has preferably been wetted, generally with water, and thenrinsed off. Application to the hair typically includes working theshampoo composition through the hair.

A preferred method for providing anti-microbial (especiallyanti-dandruff) efficacy with a shampoo embodiment comprises the stepsof: (a) wetting the hair with water, (b) applying an effective amount ofthe anti-microbial shampoo composition to the hair, and (c) rinsing theanti-microbial shampoo composition from the hair using water. Thesesteps may be repeated as many times as desired to achieve the cleansing,conditioning, and anti-microbial/anti-dandruff benefits sought.

It is also contemplated that when the anti-microbial active employed iszinc pyrithione, and/or if other optional hair growth regulating agentsare employed, the anti-microbial compositions of the present invention,may, provide for the regulation of growth of the hair. The method ofregularly using such shampoo compositions comprises repeating steps a,b, and c (above).

A further embodiment of the present invention comprises a methodcomprising the steps of (a) wetting the hair with water, (b) applying aneffective amount of a shampoo composition comprising pyrithione or apolyvalent metal salt of pyrithione, (c) rinsing the shampoocompositions from the hair using water; (d) applying an effective amountof a conditioner composition comprising a zinc containing materialaccording to the present invention; (e) rinsing the conditionercomposition from the hair using water. A preferred embodiment of theabove mentioned method includes a shampoo composition comprising zincpyrithione and a conditioner composition comprising furametpyr.

A further embodiment of the present invention comprises a method oftreating athlete's foot microbial infections, improving the appearanceof a scalp, fungal infections, dandruff, diaper dermatitis, candidiasis,treating tinea capitis, yeast infections, and onychomycosis, eachcomprising the use of the composition according to the presentinvention.

P. EXAMPLES

The following examples further describe and demonstrate the preferredembodiments within the scope of the present invention. The examples aregiven solely for the purpose of illustration, and are not to beconstrued as limitations of the present invention since many variationsthereof are possible without departing from its scope.

The composition of the invention can be made by mixing furametpyr andone or more metal salts of pyrithione in an appropriate media orcarrier, or by adding the individual components separately to the skinor hair cleansing compositions. Useful carriers are discussed more fullyabove.

1. Topical Compositions

All exemplified compositions can be prepared by conventional formulationand mixing techniques. Component amounts are listed as weight percentsand exclude minor materials such as diluents, filler, and so forth. Thelisted formulations, therefore, comprise the listed components and anyminor materials associated with such components. As used herein,“minors” refers to those optional components such as preservatives,viscosity modifiers, pH modifiers, fragrances, foam boosters, and thelike. As is apparent to one of ordinary skill in the art, the selectionof these minors will vary depending on the physical and chemicalcharacteristics of the particular ingredients selected to make thepresent invention as described herein. Other modifications can beundertaken by the skilled artisan without departing from the spirit andscope of this invention. These exemplified embodiments of theanti-microbial shampoo, anti-microbial conditioner, anti-microbialleave-on tonic, and anti-microbial foot powder compositions of thepresent invention provide excellent anti-microbial efficacy.

Q. METHODS OF MANUFACTURE FOR SHAMPOO COMPOSITIONS

The compositions of the present invention may be prepared by any knownor otherwise effective technique, suitable for providing ananti-microbial composition provided that the resulting compositionprovides the excellent anti-microbial benefits described herein. Methodsfor preparing the anti-dandruff and conditioning shampoo embodiments ofthe present invention include conventional formulation and mixingtechniques. A method such as that described in U.S. Pat. No. 5,837,661,could be employed, wherein the anti-microbial agent of the presentinvention would typically be added in the same step as the siliconepremix is added in the U.S. Pat. No. 5,837,661 description.

Antimicrobial Shampoo Examples 1-45

A suitable method for preparing the anti-microbial shampoo compositionsdescribed in Examples 1-45 (below) follows:

About one-third to all of the sodium laureth sulfate (added as 29 wt %solution) and acid are added to a jacketed mix tank and heated to about60° C. to about 80° C. with slow agitation to form a surfactantsolution. The pH of this solution is about 3 to about 7. Sodiumbenzoate, Cocoamide MEA and fatty alcohols, (where applicable), areadded to the tank and allowed to disperse. Ethylene glycol distearate(“EGDS”) is added to the mixing vessel and allowed to melt (whereapplicable). After the EGDS is melted and dispersed, Kathon CG is addedto the surfactant solution. The resulting mixture is cooled to about 25°C. to about 40° C. and collected in a finishing tank. As a result ofthis cooling step, the EGDS crystallizes to form a crystalline networkin the product (where applicable). The remainder of the sodium laurethsulfate and other components, including the silicone and anti-microbialagent(s), are added to the finishing tank with agitation to ensure ahomogeneous mixture. Polymers (cationic or nonionic) are dispersed inwater or oils as an about 0.1% to about 10% dispersion and/or solutionand can be added to the main mix, final mix, or both. Basic ZincCarbonate or other zinc-containing layered material can be added to apremix of surfactants or water with or without the aid of a dispersingagent via conventional powder incorporation and mixing techniques intothe final mix. Once all components have been added, additional viscositymodifiers, such as sodium chloride and/or sodium xylenesulfonate may beadded, as needed, to adjust product viscosity to the extent desired.Product pH can be adjusted, using an acid such as hydrochloric acid, toan acceptable value.

Antimicrobial Shampoo Compositions - Components Example 1 Example 2Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9Sodium Laureth 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 SulfateSodium Lauryl 6.00 6.00 6.00 6.00 2.00 6.00 6.00 6.00 6.00 Sulfate DecylGlucoside 10.00 EGDS 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 CMEA0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 Cetyl Alcohol0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 Guar Hydroxy 0.5000.500 0.500 0.500 0.500 0.500 0.500 0.500 0.500 Propyl TrimoniumChloride (1) Dimethicone (2) 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.850.85 ZPT (3) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.50 1.75 Furametpyr1.00 1.00 1.00 1.00 1.00 0.20 2.00 0.50 2.00 Basic Zinc 1.61 1.61 3.221.61 1.61 Carbonate (4) Zinc Hydroxy 2.00 Sulfate (5) Zinc Hydroxy 1.88Nitrate (5) Zinc Hydroxy 1.63 Chloride (5) Zinc Hydroxy 2.40 LaurylSulfate (5) Hydrochloric 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42Acid (6) Magnesium 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 SulfateSodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.750 0.750 0.750 0.7500.750 0.750 Sodium Benzoate 0.250 0.250 0.250 0.250 0.250 0.250 0.2500.250 0.250 Kathon 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.00080.0008 0.0008 Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.0225 0.02250.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.(1) Guar having a molecular weight of about 400,000, and having a chargedensity of about 0.84 meq/g, available from Aqualon. (2) Viscasil 330Mavailable from General Electric Silicones (3) ZPT having an averageparticle size of about 2.5 μm, available from Arch/Olin. (4) Basic ZincCarbonate Available from Bruggemann Chemical (5) Materials made byreported methods in Lagaly, G.; et al. Inorg. Chem. 1993, 32, 1209-1215& Morioka, H.; et al. Inorg. Chem. 1999, 38, 4211-4216 (6) 6N HCl,available from J. T. Baker, adjustable to achieve target pH ExampleExample Example Example Example Example Example Example ExampleComponents 10 11 12 13 14 15 16 17 18 Sodium Laureth 10.00 10.00 10.0010.00 10.00 10.00 10.00 10.00 10.00 Sulfate Sodium Lauryl 6.00 6.00 6.006.00 6.00 6.00 6.00 6.00 6.00 Sulfate Cocamidopropyl Betaine EGDS 1.501.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 0.800 0.8000.800 0.800 0.800 0.800 0.800 Cetyl Alcohol 0.600 0.600 0.600 0.6000.600 0.600 0.600 0.600 0.600 Guar Hydroxy 0.500 0.500 0.500 0.500 0.5000.500 0.500 0.500 0.500 Propyl Trimonium Chloride (1) Dimethicone (2)0.85 0.85 0.85 0.85 0.85 1.00 1.35 1.60 Dimethicone (3) 1.00 ZPT (4)2.00 0.50 2.00 2.00 2.00 1.00 1.00 1.00 1.00 Furametpyr 2.00 0.50 2.002.00 2.00 1.00 1.00 1.00 1.00 Basic Zinc 3.22 1.61 1.61 0.40 0.80 1.611.61 1.61 1.61 Carbonate (5) Hydrochloric Acid 0.42 0.42 0.42 0.42 0.420.42 0.42 0.42 0.42 (6) Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28 0.280.28 0.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 Sodium Xylenesulfonate Perfume 0.750 0.300 0.750 0.750 0.7500.750 0.750 0.750 1.00 Sodium Benzoate 0.250 0.250 0.250 0.250 0.2500.250 0.250 0.250 0.250 Kathon 0.0008 0.0008 0.0008 0.0008 0.0008 0.00080.0008 0.0008 0.0008 Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.02250.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. (1) Guar having a molecular weight of about 400,000, andhaving a charge density of about 0.84 meq/g, available from Aqualon. (2)Viscasil 330M available from General Electric Silicones (3) 1664Emulsion available from Dow Corning (4) ZPT having an average particlesize of about 2.5 μm, available from Arch/Olin. (5) Basic Zinc CarbonateAvailable from Bruggemann Chemical 6N HCl, available from J. T. Baker,adjustable to achieve target pH Example Example Example Example ExampleExample Example Example Example Components 19 20 21 22 23 24 25 26 27Sodium Laureth 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00Sulfate Sodium Lauryl 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00Sulfate EGDS 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 CMEA 1.6001.600 0.800 0.800 1.600 0.800 0.800 0.800 0.800 Cetyl Alcohol 0.6000.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 Guar Hydroxy 0.500 0.4000.500 0.500 0.500 0.500 Propyl Trimonium Chloride (1) Guar Hydroxy 0.500Propyl Trimonium Chloride (2) Guar Hydroxy 0.500 0.500 Propyl TrimoniumChloride (3) PEG-7M (4) 0.200 0.100 PEG-14M (5) 0.200 PEG-45M (6) 0.200Dimethicone (7) 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 ZPT (8)1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Furametpyr 0.20 1.00 1.001.00 1.00 1.00 0.50 1.00 1.00 Basic Zinc 1.61 1.61 1.61 1.61 1.61 1.611.61 1.61 Carbonate (9) Hydrochloric Acid 0.42 0.42 0.42 0.42 0.42 0.420.42 0.42 (10) Magnesium 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 SulfateSodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.800Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.750 0.750 0.750 0.7500.750 0.750 Sodium Benzoate 0.250 0.250 0.250 0.250 0.250 0.250 0.2500.250 0.250 Kathon 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.00080.0008 0.0008 Benzyl Alcohol 0.0225 0.0225 0.0225 0.0225 0.0225 0.02250.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.(1) Guar having a molecular weight of about 400,000, and having a chargedensity of about 0.84 meq/g, available from Aqualon. (2) Guar having amolecular weight of about 600,000, and having a charge density of about2.0 meq/g, available from Aqualon (3) Jaguar C-17, available from Rhodia(4) Polyox WSR N-750, available from Amerchol (5) Polyox WSR N-3000,available from Amerchol (6) Polyox WSR N-60K, available from Amerchol(7) Viscasil 330M available from General Electric Silicones (8) ZPThaving an average particle size of about 2.5 μm, available fromArch/Olin. (9) Basic Zinc Carbonate Available from Bruggemann Chemical(10) 6N HCl, available from J. T. Baker, adjustable to achieve target pHExample Example Example Example Example Example Example Example ExampleComponents 28 29 30 31 32 33 34 35 36 Sodium Laureth 10.00 12.50 14.0010.00 10.00 10.00 10.00 10.00 10.00 Sulfate Sodium Lauryl 6.00 1.50 6.006.00 6.00 6.00 6.00 6.00 6.00 Sulfate Cocamidopropyl 2.00 2.70 BetaineEGDS 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 0.8001.600 1.600 1.600 1.600 0.800 0.800 Cetyl Alcohol 0.600 0.600 0.6000.600 0.600 0.600 0.600 0.600 Guar Hydroxy 0.500 0.500 0.500 0.500Propyl Trimonium Chloride (1) Polyquaterium- 0.500 0.500 10 (2)Polyquaterium- 0.500 0.500 0.400 10 (3) PEG.7M (4) 0.200 0.100Dimethicone (5) 0.85 0.85 0.85 0.85 1.40 0.85 1.40 1.40 1.40 ZPT (6)1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Furametpyr 1.00 1.00 1.001.00 1.00 1.00 1.00 1.00 1.00 Basic Zinc 1.61 1.61 1.61 1.61 1.61 1.611.61 1.61 1.61 Carbonate (7) Hydrochloric 0.42 0.42 0.42 0.42 0.42 0.420.42 0.42 0.42 Acid (8) Magnesium 0.28 0.28 0.28 0.28 0.28 0.28 0.280.28 0.28 Sulfate Sodium 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.8000.800 Chloride Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.7500.750 0.750 0.750 0.750 0.750 Sodium 0.250 0.250 0.250 0.250 0.250 0.2500.250 0.250 0.250 Benzoate Kathon 0.0008 0.0008 0.0008 0.0008 0.00080.0008 0.0008 0.0008 0.0008 Benzyl Alcohol 0.0225 0.0225 0.0225 0.02250.0225 0.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. Q.S. (1) Guar having a molecular weight of about 400,000, andhaving a charge density of about 0.84 meq/g, available from Aqualon. (2)UCARE Polymer JR 30M, available from Amerchol (3) UCARE Polymer LR 400,available from Amerchol (4) POLYOX WSR N-750, available from Amerchol(5) Viscasil 330M available from General Electric Silicones (6) ZPThaving an average particle size of about 2.5 μm, available fromArch/Olin. (7) Basic Zinc Carbonate Available from Bruggemann Chemical(8) 6N HCl, available from J. T. Baker, adjustable to achieve target pHExample Example Example Example Example Example Example Example ExampleComponents 37 38 39 40 41 42 43 44 45 Sodium Laureth 10.00 10.00 10.0010.00 10.00 10.00 10.00 10.00 10.00 Sulfate Sodium Lauryl 6.00 6.00 6.006.00 6.00 6.00 6.00 6.00 6.00 Sulfate EGDS 1.50 1.50 1.50 1.50 1.50 1.501.50 1.50 1.50 CMEA 1.600 1.600 1.600 1.600 1.600 1.600 1.600 1.6001.600 Cetyl Alcohol 0.600 0.600 0.600 0.600 0.600 0.600 0.600 0.6000.600 Guar Hydroxy 0.400 0.400 0.400 0.400 0.400 0.400 0.400 PropylTrimonium Chloride (1) Polyquaterium- 0.500 0.250 0.100 0.100 0.1000.100 0.100 0.100 0.100 10 (2) PEG-7M (3) 0.100 0.100 0.100 0.100 0.1000.100 0.100 0.100 Dimethicone (4) 0.85 0.85 0.85 0.85 0.85 0.85 0.850.85 0.85 ZPT (5) 1.00 1.00 1.00 Furametpyr 1.00 1.00 1.00 1.00 1.001.00 1.00 1.00 1.00 Ketoconazole 1.00 Climbazole 1.00 Octopirox 1.00Salicylic acid 1.00 Coal tar 1.00 Selenium sulfide 1.00 Basic Zinc 1.611.61 Carbonate (6) Hydrochloric 0.42 0.42 0.42 Acid (7) MagnesiumSulfate 0.28 0.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.8000.800 0.800 0.800 0.800 Sodium Xylenesulfonate Perfume 0.750 0.750 0.7500.750 0.750 0.750 0.750 0.750 0.750 Sodium 0.250 0.250 0.250 0.250 0.2500.250 0.250 0.250 0.250 Benzoate Kathon 0.0008 0.0008 0.0008 0.00080.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol 0.0225 0.0225 0.02250.0225 0.0225 0.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. (1) Guar having a molecular weight of about 400,000,and having a charge density of about 0.84 meq/g, available from Aqualon.(2) UCARE Polymer LR 400, available from Amerchol (3) POLYOX WSR N-750,available from Amerchol (4) Viscasil 330M available from GeneralElectric Silicones (5) ZPT having an average particle size of about 2.5μm, available from Arch/Olin. (6) Basic Zinc Carbonate Available fromBruggemann Chemical (7) 6N HCl, available from J. T. Baker, adjustableto achieve target pH10. Other Ingredients

The present invention may, in some embodiments, further compriseadditional optional components known or otherwise effective for use inhair care or personal care products. The concentration of such optionalingredients generally ranges from zero to about 25%, more typically fromabout 0.05% to about 20%, even more typically from about 0.1% to about15%, by weight of the composition. Such optional components should alsobe physically and chemically compatible with the essential componentsdescribed herein, and should not otherwise unduly impair productstability, aesthetics or performance.

Non-limiting examples of optional components for use in the presentinvention include anti-static agents, foam boosters, anti-dandruffagents in addition to the anti-dandruff agents described above,viscosity adjusting agents and thickeners, suspension materials (e.g.EGDS, thixins), pH adjusting agents (e.g. sodium citrate, citric acid,succinic acid, sodium succinate, sodium maleate, sodium glycolate, malicacid, glycolic acid, hydrochloric acid, sulfuric acid, sodiumbicarbonate, sodium hydroxide, and sodium carbonate), preservatives(e.g. DMDM hydantoin), anti-microbial agents (e.g. triclosan ortriclocarbon), dyes, organic solvents or diluents, pearlescent aids,perfumes, fatty alcohols, proteins, skin active agents, sunscreens,vitamins (such as retinoids including retinyl propionate, vitamin E suchas tocopherol acetate, panthenol, and vitamin B3 compounds includingniacinamide), emulsifiers, volatile carriers, select stability actives,styling polymers, organic styling polymers, silicone-grafted stylingpolymers, cationic spreading agents, pediculocides, foam boosters,viscosity modifiers and thickeners, polyalkylene glycols andcombinations thereof.

Optional anti-static agents such as water-insoluble cationic surfactantsmay be used, typically in concentrations ranging from about 0.1% toabout 5%, by weight of the composition. Such anti-static agents shouldnot unduly interfere with the in-use performance and end-benefits of theanti-microbial composition; particularly, the anti-static agent shouldnot interfere with the anionic surfactant. A specific non-limitingexample of a suitable anti-static agents is tricetyl methyl ammoniumchloride.

Optional foam boosters for use in the present invention described hereininclude fatty ester (e.g. C₈-C₂₂) mono- and di(C₁-C₅, especially C₁-C₃)alkanol amides. Specific non-limiting examples of such foam boostersinclude coconut monoethanolamide, coconut diethanolamide, and mixturesthereof.

Optional viscosity modifiers and thickeners may be used, typically inamounts effective for the anti-microbial compositions of the presentinvention to generally have an overall viscosity from about 1,000 csk toabout 20,000 csk, preferably from about 3,000 csk to about 10,000 csk.Specific non-limiting examples of such viscosity modifiers andthickeners include: sodium chloride, sodium sulfate, and mixturesthereof.

R. OTHER PREFERRED EMBODIMENTS

Other preferred embodiments of the present invention include thefollowing:

An embodiment of the present invention, relates to the composition maybe employed to treat a variety of conditions, including: athlete's foot,microbial infections, improving the appearance of a scalp, treatingfungal infections, treating dandruff, treating diaper dermatitis andcandidiasis, treating tinea capitis, treating yeast infections, treatingonychomycosis. Preferably, such conditions are treated by applying acomposition of the present invention to the affected area.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A composition comprising: a) an effective amountof a pyrithione or a polyvalent metal salt of a pyrithione; b) aneffective amount of furametpyr; and c) an effective amount of asurfactant with an anionic functional group.
 2. A composition accordingto claim 1 wherein the pyrithione or polyvalent metal salt of pyrithioneis zinc pyrithione.
 3. A composition according to claim 2 wherein thezinc pyrithione is present from about 0.01% to about 5%.
 4. Acomposition according to claim 1 wherein furametpyr is present fromabout 0.1% to about 2.0%.
 5. A composition according to claim 1 whereinfurametpyr is present from about 0.2% to about 1.5%.
 6. A compositionaccording to claim 1 wherein the surfactant with an anionic functionalgroup is about 1% to about 50% of the total composition.
 7. Acomposition according to claim 1 wherein the surfactant with an anionicfunctional group is present from about 2% to about 50%.
 8. A compositionaccording to claim 7 further comprising a surfactant selected from thegroup consisting of cationic, nonionic, amphoteric or zwitterionic.
 9. Acomposition according to claim 1 wherein the pH is greater than about6.5.
 10. A composition according to claim 9 wherein the pH is from about6.8 to about 9.5.
 11. A composition according to claim 10 wherein the pHis from about 6.8 to about 8.5.
 12. A composition according to claim 1wherein the composition further comprises a particulate zinc material.13. A composition according to claim 12 wherein the particulate zincmaterial has a relative zinc lability of greater than about 15%.
 14. Acomposition according to claim 13 wherein the particulate zinc materialhas a relative zinc lability of greater than about 20%.
 15. Acomposition according to claim 14 wherein the particulate zinc materialhas a relative zinc lability of greater than about 25%.
 16. Acomposition according to claim 12 wherein the particulate zinc materialis selected from the group consisting of inorganic materials, naturalzinc sources, ores, minerals, organic salts, polymeric salts, orphysically adsorbed from material and mixtures thereof.
 17. Acomposition according to claim 16 wherein the inorganic materials isselected from the group consisting of zinc aluminate, zinc carbonate,zinc oxide, calamine, zinc phosphate, zinc selenide, zinc sulfide, zincsilicates, zinc silicofluoride, zinc borate, or zinc hydroxide and zinchydroxy sulfate, zinc-containing layered material and mixtures thereof.18. A composition according to claim 17 the zinc-containing layeredmaterial is selected from the group consisting of basic zinc carbonate,zinc carbonate hydroxide, hydrozincite, zinc copper carbonate hydroxide,aurichalcite, copper zinc carbonate hydroxide, rosasite, phyllosilicatecontaining zinc ions, layered double hydroxide, hydroxy double salts andmixtures thereof.
 19. A composition according to claim 18 wherein thezinc-containing layered material is selected from the group consistingof zinc carbonate hydroxide, hydrozincite, basic zinc carbonate andmixtures thereof.
 20. A composition according to claim 19 wherein thezinc-containing layered material is hydrozincite or basic zinccarbonate.
 21. A composition according to claim 20 wherein thezinc-containing layered material is basic zinc carbonate.
 22. Acomposition according to claim 1 wherein the composition furthercomprises a cationic deposition polymer.
 23. A composition according toclaim 1 wherein the composition comprises less than 5.5 micromoles of azinc binding material per gram of the particulate zinc material/perm²/gram surface area of the particulate zinc material.
 24. A compositionaccording to claim 23 wherein the zinc binding material is selected fromthe group comprising laurate, citrate, valerate, oxalate, tartrate,iodate, thiocyanate, cyanide, sulfide, pyrophosphate, phosphate andmixtures thereof.
 25. A composition according to claim 24 wherein thezinc binding material is laurate.
 26. A composition according to claim 1wherein the composition further comprises a conditioning agent.
 27. Acomposition according to claim 1 wherein the composition furthercomprises a suspending agent.
 28. A composition according to claim 27wherein the suspending agent is selected from the group consisting ofcrystalline suspending agent, polymeric suspending agent or mixturesthereof.
 29. A composition according to claim 28 wherein the suspendingagent is a crystalline suspending agent.
 30. A composition according toclaim 1 wherein the composition comprises an additional surfactant foruse in combination with the surfactant with an anionic functional group.31. A composition according to claim 30 wherein the additional surfacantis selected from the group consisting of cationic, nonionic and mixturesthereof.
 32. A composition comprising: a) an effective amount of apyrithione or a polyvalent metal salt of a pyrithione; b) an effectiveamount of furametpyr; and c) an effective amount of a surfactant with ananionic functional group; wherein the composition is applied to theskin.
 33. A method of treating dandruff comprising the step of applyingthe composition of claim 1 to the skin or scalp.